Synthesis and Radical Polymerization of a Novel Macromonomer Obtained by Living Cationic Ring-Opening Polymerization of an Optically Active Cyclic Thiourethane by a New Initiator Carrying Styryl Group
Synthesis and Radical Polymerization of a Novel Macromonomer Obtained by Living Cationic Ring-Opening Polymerization of an Optically Active Cyclic Thiourethane by a New Initiator Carrying Styryl Group
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带有苯乙烯基的新型引发剂对光学活性环状硫代氨基甲酸酯进行活性阳离子开环聚合得到新型大分子单体的合成和自由基聚合
DOI：
10.1021/ma040009b
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发表时间：
2004
期刊：
影响因子：
5.5
通讯作者：
T. Endo
中科院分区：
文献类型：
--
作者：
A. Nagai;Bungo Ochiai;T. Endo
以1,3-恶唑烷-2-硫酮衍生物与甲基三氟甲烷磺酸为原料，定量合成了一种新型阳离子引发剂-4-乙烯基苯甲酸-2-甲基磺酰-4,5-二氢恶唑啉-4-基甲酯三氟甲烷磺酸盐(1)，该引发剂同时带有乙烯基和三氟磺酸基。以l-丝氨酸为原料，以1为引发剂，在二氯甲烷中进行了活性阳离子开环聚合反应，得到了相应的高分子单体（MSL; Mn > 104, Mw/Mn < 1.18）， MSL的分子量可由[SL]/[1]控制。MSL由旋光性硫脲主链和引发端苯乙烯基定量组成。对MSL进行了自由基均聚和与苯乙烯的共聚，得到了相应的高产率聚合物。与MSL相比，MSL获得的聚合物具有更高的比旋光度（[α]25D）、熔点（Tm）和棉花效应，支持了MSL的稳定性。
A new cationic initiator, 4-vinylbenzoic acid 2-methylsulfanyl-4,5-dihydrooxazolinium-4-ylmethyl ester trifluoromethanesulfonate (1), carrying both vinyl and triflate groups, was synthesized in quantitative yield by reaction of 1,3-oxazolidine-2-thione derivative with methyl trifluoromethanesulfonate. Living cationic ring-opening polymerization of an optically active cyclic thiourethane (SL) derived from l-serine was carried out by with 1 as an initiator in dichloromethane to give the corresponding macromonomers (MSL; Mn > 104, Mw/Mn < 1.18), and the molecular weight of MSL could be controlled by [SL]/[1]. MSL consists of the optically active thiourethane main chain and styryl group in the initiating end quantitatively. The radical homopolymerization of MSL and the copolymerization with styrene were carried out to obtain the corresponding polymers in higher yields. The obtained polymer from MSL showed higher specific rotation ([α]25D), melting point (Tm), and Cotton effect than MSL, supporting the stabili...